JP2007269003A - Half-curing resin sheet with pattern and molded article using the half-curing resin sheet with pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flexible half-curing resin sheet with a pattern which has excellent followability to a mold, and also to provide a molded product with the pattern using the half-curing resin sheet with the pattern. <P>SOLUTION: The half-curing resin sheet with the pattern comprises a clear resin layer, a reinforcement layer, and a pattern layer or a transfer pattern layer, or a pattern fixing layer added to these, wherein the degree of curing of the clear resin layer is 5-80%, and the maximum exothermic peak temperature when carrying out DSC measurement of the clear resin layer forming composition at the temperature increasing speed of 10°C/min is 110-180°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a patterned semi-cured resin sheet and a molded article using the patterned semi-cured resin sheet, and particularly relates to a molded article that is a bathroom component.

In recent years, in order to improve the design of the bathroom component, etc., a molded product with a pattern having a pattern on the surface has been proposed. In more detail, in order to obtain a patterned product, a semi-cured resin sheet with a pattern manufactured in the following steps (1) to (4) has been proposed.
(1) A pattern layer is formed on a clear film.
(2) After a clear film, a pattern layer, a woven fabric and / or a non-woven fabric are stacked, a thermosetting resin to which an organic peroxide is added is placed in a lump shape, and further a clear film is stacked.
(3) The woven fabric and / or the non-woven fabric is impregnated with a clear resin while rolling and pressing from the end with a roller to uniformly stretch and degas.
(4) A semi-cured state is obtained by heating, and the clear film is peeled off.
The patterned molded product can be obtained by heating and pressurizing the patterned semi-cured resin sheet obtained through the above steps (1) to (4) integrally with a molding material such as SMC (Patent Document 1).

The semi-cured resin sheet with a pattern described in Patent Document 1 has an advantage that a molded product can be efficiently manufactured because the pattern and the sheet shape can be easily maintained and handled.
In addition, it has a strength that does not cause outflow, crack breakage, etc., against the flow of SMC during pressure-heat integrated molding, and it is a reactive group that allows adhesion to the molding material during complete curing. Therefore, adhesion to the molding material can be secured.

Furthermore, a method has also been proposed in which a patterned semi-cured resin sheet and a molding material are overlapped and integrated by pressure and heat molding (Patent Document 2).
Japanese Patent Laid-Open No. 06-134785 Japanese Patent Laid-Open No. 06-134784

The surface of the washing floor of the waterproof pan, which is a bathroom component, has been subjected to fine unevenness processing, matting processing, fine drainage groove processing, and the like according to customer requirements such as drainage, dryness, and non-slip properties (preventing toppling). Along with this, the surface shape of the surface mold is also changed to finer unevenness and matte shape as compared with the conventional surface mold.
However, the above-described method has a problem that sufficient transferability cannot be obtained for a fine and complicated surface shape.

  This is because the method described above uses an organic peroxide that decomposes at a relatively low temperature in order to obtain a semi-cured state, so that a patterned semi-cured resin sheet and a molding material are integrally formed by pressure and heating. In this case, immediately after the patterned semi-cured resin sheet is placed on the high-temperature surface mold, the remaining portion of the low-temperature decomposition type organic peroxide is subjected to thermal decomposition and the curing proceeds rapidly. This is because the patterned semi-cured resin sheet becomes hard before sufficient transferability is obtained.

  The present invention solves the above-described problems, and provides a patterned semi-cured resin sheet that has good mold followability and flexibility, and a patterned molded article using the patterned semi-cured resin sheet. The purpose is to do.

The present invention relates to the following.
(1) A clear resin layer, a reinforcing layer, a pattern layer or a transfer pattern layer, or a pattern fixing layer thereon, wherein the clear resin layer has a degree of cure of 5 to 80%, and a clear resin layer forming composition A patterned semi-cured resin sheet having a maximum exothermic peak temperature of 110 to 180 ° C. when DSC is measured at a heating rate of 10 ° C./min.
(2) The patterned semi-cured resin sheet according to item (1), wherein the clear resin layer contains a thermosetting resin, an organic peroxide, and ascorbic acid.
(3) The patterned semi-cured resin sheet according to item (2), wherein the clear resin layer is in a semi-cured state at 30 to 100 ° C. and then cooled to 10 ° C. or less.
(4) The patterned semi-cured resin sheet according to item (1), wherein the clear resin layer contains a thermosetting resin, an organic peroxide, ascorbic acid, and a chain transfer agent.
(5) The patterned semi-cured resin sheet according to item (4), wherein the clear resin layer is semi-cured at 0 to 100 ° C.
(6) The patterned semi-cured resin sheet according to any one of items (1) to (5), wherein the reinforcing layer is formed by impregnating a woven fabric or a nonwoven fabric with a clear resin layer forming composition.
(7) The patterned semi-cured resin sheet according to any one of items (1) to (6), wherein the pattern layer is formed by gravure printing or inkjet printing.
(8) The patterned semi-cured resin sheet according to any one of items (1) to (7), wherein the pattern layer or the transfer pattern layer is formed by laminating a glass fiber nonwoven fabric or a synthetic resin nonwoven fabric on the surface opposite to the reinforcing layer.
(9) A molded product obtained by laminating a patterned semi-cured resin sheet described in any one of items (1) to (8) on an SMC, and pressurizing and heating integrally.
(10) In item (9), SMC is a fiber reinforced compound containing a thermosetting resin, a polymerizable monomer, a low shrinkage agent, an organic peroxide, a polymerization inhibitor, a filler and a thickener. A fiber-reinforced molding material impregnated with a material, which is formed into a sheet.
(11) A molded product according to item (9) or (10), wherein the molded product has fine irregularities on a part or all of its surface.
(12) A molded product according to any one of items (9) to (11), wherein the molded product is a bathroom component.
(13) The molded product according to any one of items (9) to (12), wherein a glass fiber nonwoven fabric or a synthetic resin nonwoven fabric is disposed between the patterned semi-cured resin sheet and the SMC.

  According to the present invention, it is possible to obtain a patterned semi-cured resin sheet having good followability to the surface shape of a mold, transferability to fine irregularities, and excellent flexibility, and the patterned semi-cured of the present invention. The molded product with a pattern using a resin sheet has no pattern limitation and the pattern is clear.

  As shown in FIG. 1, the patterned molded product obtained from the patterned semi-cured resin sheet and the molding material in the present invention has a clear resin layer 1, a reinforcing layer 2, a pattern layer 6 or a transfer pattern layer 3, and a base, as shown in FIG. A structure provided with the material layer 4 or the pattern fixing layer 5 is preferable.

  The clear resin layer in the present invention is formed by semi-curing and completely curing a thermosetting resin, an organic peroxide, ascorbic acid, or a composition obtained by blending a chain transfer agent therewith.

  Although there is no restriction | limiting in particular as a thermosetting resin, It is preferable to use unsaturated polyester resin, and thermosetting resins, such as a vinyl ester resin, an acrylic resin, and a diallyl phthalate resin, can use 2 or more types of resin. You may use together.

  As the unsaturated polyester resin, it is possible to use an unsaturated polybasic acid, a saturated polybasic acid, and a polyhydric alcohol that are dehydrated and condensed at a specific ratio and mixed with a polymerizable monomer.

  Examples of the unsaturated polybasic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides thereof. Two or more of these may be used in combination.

  Saturated polybasic acids or anhydrides thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydro Examples thereof include phthalic anhydride, glutaric acid, adipic acid, sebacic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, dimer acid, succinic acid, azelaic acid, and rosin-maleic acid adduct. Two or more of these may be used in combination.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and hydrogenated bisphenol A. And trihydric alcohols such as monohydric alcohol, glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol. Two or more of these may be used in combination.

  Examples of the polymerizable monomer include styrene derivatives such as styrene, chlorostyrene, divinylbenzene, tertiary butyl styrene and styrene bromide, and methacrylic acid such as methyl methacrylate, ethyl methacrylate, ethyl acrylate and butyl acrylate. Alternatively, an alkyl ester of acrylic acid, a hydroxyalkyl ester of methacrylic acid or acrylic acid such as ethyl β-hydroxymethacrylate or ethyl β-hydroxyacrylate, diallyl phthalate, acrylamide, phenylmaleimide, or the like can be given. In addition, polyfunctional methacrylic acid or acrylic acid esters such as ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethyl propane trimethacrylate can be used.

The organic peroxide is for completely curing the thermosetting resin at the time of pressure heating integrated molding, and the clear resin layer forming composition to which the organic peroxide is added is subjected to DSC at a temperature rising rate of 10 ° C./min. The maximum exothermic peak temperature at the time of measurement may be 110 ° C. to 180 ° C., and one or two or more types can be used in combination, and the combination and type can be selected according to the application, so almost all Organic peroxides can be used.
When an organic peroxide having a maximum exothermic peak temperature of less than 110 ° C when measured by DSC is used, the progress of the reaction is gradually accelerated during pressure heating integrated molding, and depending on the surface shape of the mold, there is a possibility of causing a transfer failure. Go up gradually.
Further, if the maximum exothermic peak temperature exceeds 180 ° C., there is a possibility that poor curing may occur gradually at the time of pressure-heat integrated molding, and the molding time becomes gradually longer, which is not preferable.
Organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, dialkylperoxydicarbonates, peroxyesters, etc. In addition, peroxides can be used.
The total amount of the organic peroxide can be appropriately set according to the use and conditions, but is 0.1 to 5.0 parts by mass, preferably 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the thermosetting resin. It is the range of 2 mass parts-3.0 mass parts. If the amount of the organic peroxide is less than 0.1 parts by mass, the possibility that the thermosetting resin is in an incompletely cured state gradually increases, and if it exceeds 5.0 parts by mass, it is gradually economically It will be disadvantageous.

  Ascorbic acid may be L-ascorbic acid, D-ascorbic acid or a derivative thereof, or may be a mixture thereof, and industrially produced ascorbic acid can be used. Ascorbic acid has a function of making the thermosetting resin into a semi-cured state, and when the heat-pressed integrated molding is carried out, the curing proceeds even if the patterned semi-cured resin sheet is placed on a high-temperature surface mold. Therefore, sufficient transferability can be obtained even in a fine and complicated shape.

Since ascorbic acid is usually a needle-like crystal, it can be used in a crystalline state or as an organic solvent solution, but it is preferably used as an organic solvent solution from the viewpoint of handling. Examples of usable organic solvents include various organic esters such as ketones, phthalic acid esters, and phosphoric acid esters, alcohols, alkylene glycols, and various aliphatic hydrocarbons, and can also be used as an aqueous solution. . A particularly preferable organic solvent is triethyl phosphate having excellent solubility in ascorbic acid. The solution concentration is preferably about 5 to 30%. This is because if the amount is less than 5%, the amount of the organic solvent to be used gradually increases, which is economically disadvantageous. Conversely, if it exceeds 30%, the time required to dissolve ascorbic acid gradually increases.

  Although the compounding quantity of ascorbic acid can be suitably set according to a use and a desired semi-hardened state, it is 0.001-1.0 mass part as an ascorbic acid with respect to 100 mass parts of thermosetting resins, Preferably 0.01 to 0.5 parts by mass. This is because if the amount of ascorbic acid is too small, the time until the semi-cured state becomes longer, and conversely if too much, the transition from the semi-cured state to the fully cured state may occur, and the patterned semi-cured resin sheet may be discolored. Because there is.

  The chain transfer agent is used for adjusting the semi-cured state and maintaining stable for a long time. For example, 2,4-diphenyl 4-methyl 1-pentene or terpinolene can be used alone or in combination. As a method for adjusting the semi-cured state and maintaining stable for a long time, there is a method of cooling to 10 ° C. or lower after semi-curing, especially when not using a chain transfer agent, cooling to 10 ° C. or lower. Is preferred.

  The compounding quantity of a chain transfer agent is 0.01-10 mass parts with respect to 100 mass parts of thermosetting resins, Preferably it is 0.1-3.0 mass parts. This is because if the amount of the chain transfer agent is too small, the semi-cured state may shift to the fully cured state, and conversely if too large, the time until the semi-cured state becomes long.

  Moreover, when using a chain transfer agent, if the maximum exothermic peak temperature when the clear resin layer forming composition is measured by DSC at a heating rate of 10 ° C./min is 110 to 180 ° C., the thermosetting resin is cured. In combination with organic peroxides, it is possible to use organic peroxides that react at relatively low temperatures, and due to a synergistic effect with ascorbic acid, they can be semi-cured even at relatively low temperatures. It is. Examples of the organic peroxide used in combination with ascorbic acid to achieve a semi-cured state include hydroperoxides, peroxyesters, peroxyketals, dialkylperoxydicarbonates, and ketone peroxides.

  The reinforcing layer in the present invention can be formed by impregnating a woven fabric and / or a nonwoven fabric with a clear resin layer composition. The woven fabric and / or non-woven fabric is preferably one that provides transparency after impregnation and curing with the surface-forming resin, organic fibers such as paper, polyester resin, acrylic resin, or woven fabric made of inorganic fibers such as glass, Use non-woven fabric. The woven fabric includes plain weave and twill weave, and the nonwoven fabric includes felt, mat, and paper, but is not particularly limited. In addition, two or more reinforcing layers may be provided, and different types of reinforcing materials can be used in combination. However, when forming on the product surface side with respect to the pattern layer, the sharpness of the pattern is lost as the number of reinforcing layers is increased. It is more preferable to reduce as much as possible.

The pattern layer in the present invention can be formed by patterning by printing by ink jet printing, gravure printing, screen printing, or spraying. Further, the patterning can be carried out on papers used as the reinforcing layer of the present invention, organic fibers such as polyester resins and acrylic resins, or non-woven fabrics made of inorganic fibers such as glass, and if necessary, woven fabrics and / or non-woven fabrics The ink fixing process can be applied to the ink. Also, the basis weight of the fiber ^{is preferably, 30g / m 2 ~100g / m} 2 and more preferably 15g / ^{m 2} ~250g / m 2 approximately. If the weight per unit area is less than 15 g / m ² , the ink adhesion area on the fiber surface is small, and the pattern gradually becomes rough and the sharpness tends to decrease. If it exceeds 250 g / m ² , the resin for forming the surface layer There is a tendency that the amount of use of sucrose increases gradually and the economic efficiency is impaired.

  In the formation of the transfer pattern layer in the present invention, it is preferable to use a transfer film in which a pattern layer or a pattern layer arranged on a single color layer is formed with ink on one side of the clear film. The transfer pattern layer can be formed by gravure printing, ink jet printing, screen printing, spray spraying, or the like. There are two types of printing modes: normal printing in which the pattern is formed on the side opposite to the clear film upon completion of printing, and reverse printing in which the pattern is formed on the side of the clear film. The clear film constituting the transfer film is not particularly limited as long as it has heat resistance, peelability and is insoluble in the surface resin. Plastic film such as polyethylene, polypropylene, nylon, polyester, fluorine film, aluminum foil For example, a metal foil such as a single film or another film, or a paper or plastic film coated with a releasable resin can be used.

The pattern fixing layer is formed in order to prevent the flow of the pattern layer and the transfer pattern layer at the time of pressure and heat integral molding, and can be appropriately formed depending on the use, when the surface unevenness of the mold is rough or deep, or It is effective to provide a pattern fixing layer when the shape is complicated. Normally, the pattern fixing layer can be set higher than the degree of cure of the clear resin layer, so that the pattern layer can be protected from the flow of the molding material during pressure heating integrated molding. By providing either one or both, the flow of the printing ink can be suppressed. In addition, the pattern fixing layer can be formed by using any or all of thermosetting resin, organic peroxide, ascorbic acid, chain transfer agent, reinforcing material, and the like. The degree of curing can be adjusted by adjusting the amount or curing temperature and curing time. The degree of cure is determined according to the degree of cure of the clear resin layer, the shape of the mold used, or the application, and is not particularly limited, but is preferably 20 to 95%. On the other hand, the maximum exothermic peak temperature when the pattern fixing layer forming composition is measured by DSC is not particularly limited because it is determined according to the shape of the mold to be used or the application, but is 80 to 180 ° C. Preferably there is. The pattern fixing layer may be provided in two or more layers, and may contain a reinforcing material. However, when the reinforcing material is contained, it is more preferable to form the pattern fixing layer on the side opposite to the product surface. . This is because when the number of layers on the product surface side with respect to the pattern layer increases, the sharpness of the pattern is gradually lost, and the desired color expression may become difficult.
In addition, the pattern fixing layer can be formed by placing a glass fiber nonwoven fabric or a synthetic resin nonwoven fabric between the patterned semi-cured resin sheet and the SMC at the time of pressure-heat integrated molding. In this case, the glass fiber nonwoven fabric or the synthetic resin nonwoven fabric relaxes the flow pressure during molding, prevents the flow of the pattern layer, and impregnates the thermosetting resin during molding to bind the patterned semi-cured resin sheet and SMC, A pattern fixing layer is formed between the patterned semi-cured resin sheet and the SMC.

  The thickness of the transfer film is preferably about 10 μm to 100 μm and more preferably 25 μm to 50 μm in order to uniformly stretch the surface resin. If the thickness is less than 10 μm, wrinkles are likely to occur during film handling, and the appearance of the patterned semi-cured resin sheet may be impaired. In addition, defects such as perforation are likely to occur when the surface layer forming resin is stretched by a roller, and there is a tendency that bubbles are mixed in the patterned semi-cured resin sheet.

  The ink used for the transfer film is preferably an unsaturated polyester resin, acrylic resin, epoxy resin, nitrified cotton (nitrocellulose) resin or the like mixed with a pigment or dye. The pattern may be any of wood grain, stone tone, abstract pattern, etc., and is not particularly limited.

The cross-section of the patterned molded article using the patterned semi-cured resin sheet in the present invention can be as shown in FIG. 1, and the patterned semi-cured resin sheet to be used is the following process as shown in FIGS. Can be produced.
(1) The process of forming a pattern layer on the clear film 10 or a woven fabric and / or a nonwoven fabric.
(2) A step of placing the clear resin layer forming composition 9 in a lump shape and further overlaying the clear film 10 after superposing the clear film 10, the pattern layer 6, the woven fabric and / or the non-woven fabric.
(3) A step of impregnating the woven fabric and / or the nonwoven fabric with the clear resin-forming composition 9 while uniformly stretching and defoaming by pressing from the end with a roller.
(4) A step of making the semi-cured state by heating and peeling the clear film 10.
In addition, when the surface roughness of the mold is rough or deep, or when the shape is complicated, as shown in FIG. 4, in addition to the steps (1) to (4) above, the upper and lower surfaces or both surfaces of the pattern layer A step of forming a uniform pattern fixing layer in a semi-cured state is required.

  The clear film used at the time of producing the patterned semi-cured resin sheet is not particularly limited as long as it has peelability and is insoluble in the thermosetting resin. Usually, it can be used except for a metal foil such as an aluminum foil, which is bonded to a single or other film, or an opaque material such as paper. The thickness of the film is preferably about 10 μm to 100 μm and more preferably 25 μm to 50 μm in order to uniformly stretch the surface resin.

The curing temperature for making the patterned semi-cured resin sheet semi-cured depends on the amount of thermosetting resin, organic peroxide, and ascorbic acid used and the degree of curing of the required semi-cured resin sheet. Usually, the curing temperature for semi-curing is 30 to 100 ° C., preferably 50 to 90 ° C., and then cooled to 10 ° C. or lower. This is because when the temperature exceeds 100 ° C., the semi-cured state may shift to the fully cured state, and when it is less than 30 ° C., it is inappropriate from the viewpoint of the stability of the semi-cured state. The reason for cooling to 10 ° C. or lower is to keep the semi-cured state stable for a long period of time, and it is preferable to cool immediately after curing.
Moreover, when using a chain transfer agent, if the maximum exothermic peak temperature when the clear resin layer forming composition is measured by DSC at a heating rate of 10 ° C./min is 110 to 180 ° C., the thermosetting resin is cured. In combination with organic peroxides, organic peroxides that react at relatively low temperatures can be used, and due to synergistic effects with ascorbic acid, they can be semi-cured even at low temperatures. . For this reason, when using a chain transfer agent, the curing temperature for semi-curing is 0 to 100 ° C, preferably 10 to 90 ° C.

  The curing time of the patterned semi-cured resin sheet is governed by the required degree of curing of the patterned semi-cured resin sheet, environmental conditions, etc., and thus cannot be generally specified, but it may be 2 minutes to 10 hours. it can.

  The degree of cure of the patterned semi-cured resin sheet can be appropriately set according to the use and cannot be specified unconditionally, but is about 5 to 80%, preferably 10 to 60%. If it is less than 5%, the patterned semi-cured resin sheet is sticky, and the handleability tends to decrease. Further, the strength of the patterned semi-cured resin sheet gradually becomes insufficient, and in some cases, it may be destroyed during heating and pressure molding by a press. On the other hand, if the degree of cure exceeds 80%, the fine unevenness, glossiness, followability to matte shape, and transferability of the surface mold surface during pressurization and heat molding are gradually reduced. The degree of cure is calculated by measuring the amount of monomer remaining in the patterned semi-cured resin sheet.

  In the patterned semi-cured resin sheet, a polymerization inhibitor can be used particularly for the purpose of adjusting the semi-curing speed, maximum exothermic temperature, etc., for example, p-benzoquinone, naphthoquinone, tolquinone, hydroquinone, mono-t-butyl. Examples thereof include hydroquinone and dibutylhydroxytoluene. Moreover, it is preferable that the compounding quantity is 0.01-1.0 mass part with respect to 100 mass parts of thermosetting resins.

In addition to fillers such as calcium carbonate, aluminum hydroxide glass balloons and shirasu balloons, and coloring agents such as toner and pigments, thermoplastic resins and low shrinkage agents, stearic acid are also included in the semi-cured resin sheet with patterns. Various additives such as a release agent such as zinc, an antifoaming agent, an accelerator, a silane coupling agent, a molecular sieve and a foam stabilizer can be blended in each layer.
In addition, a layer to which these additives are added can be newly added to the patterned semi-cured resin sheet in the present invention, and the number of layers to be formed is not particularly limited.

There is no particular limitation on the method of pressing at the time of preparing the patterned semi-cured resin sheet, as long as the surface layer forming resin can be uniformly defoamed and stretched over the entire surface and can be impregnated into the woven fabric and / or the nonwoven fabric. Etc. can be used.
Moreover, there is no restriction | limiting in particular as a cutting method of a semi-cured resin sheet with a pattern, but it is preferable to use a Thomson type etc. in view of cutting dimensional accuracy and productivity.

  The thickness of the patterned semi-cured resin sheet is preferably about 50 μm to 3000 μm, and more preferably 200 μm to 500 μm. If the thickness is less than 50 μm, the patterned semi-cured resin sheet tends to be gradually damaged due to the flow of the molding material during pressurization and heat molding, and if it exceeds 3000 μm, the amount of the resin for forming the surface layer is used. There is a tendency that the economy gradually increases and the economic efficiency is impaired.

  As a molding material used as the base material layer in the present invention, thermosetting fiber reinforced molding materials such as SMC, TMC, and BMC can be used.

As a method of pressure heating integrated molding, as shown in FIG. 5, a method for placing and molding a patterned semi-cured resin sheet and a molding material in order from the surface mold, or from a surface mold as shown in FIG. 6. There is a method in which a patterned semi-cured resin sheet, a nonwoven fabric, and a molding material are placed in order, and the molding pressure is about 3.98 MPa to 9.81 MPa (40 kgf / cm ^{2 to} 100 kgf / cm ² ). Is preferable, and more preferably 4.90 MPa to 7.85 MPa (50 kgf / cm ^{2 to} 80 kgf / cm ² ). When the molding pressure is less than 3.98 MPa, there is a tendency that air at the interface between the patterned semi-cured resin sheet and the molding material is difficult to escape. Moreover, it is preferable that it is about 110-170 degreeC, and, as for the surface type | mold and back surface mold temperature, it is more preferable that it is 130-160 degreeC. When the surface mold and the back mold temperature are less than 110 ° C., it takes a long time until the patterned semi-cured resin sheet and the molding material are completely cured, and the productivity tends to decrease. On the other hand, when the mold temperature for the front surface and the mold temperature for the back surface exceed 170 ° C., the curing progress of the molding material and the patterned semi-cured resin sheet is accelerated, the fine irregularities on the surface mold surface of the patterned semi-cured resin sheet, gloss, Followability to matte shape and transferability are reduced.

  Further, the fine irregularities are arbitrarily selected by setting the evaluation length to 20 mm, the measurement speed 0.6 mm / s, the cut-off value 0.08 mm, the filter type Gaussin, and the cut-off ratio 300 with a surface roughness shape measuring machine. When three or more locations are measured, the arithmetic average roughness Ra (JIS B0601-1994) is applied so that the average value is 0.5 μm or more, and more preferably 0.7 μm or more.

  Hereinafter, the present invention will be described by way of examples. In each example, SMC was used as the molding material that becomes the base layer of the patterned molded article. SMC is unsaturated polyester resin PS-9415 (trade name, manufactured by DH Material Co., Ltd.) 85 parts by mass (styrene 60 parts by mass) dissolved in styrene and 15 parts by mass of polystyrene (60 parts by mass of styrene) dissolved in styrene. Part) of organic peroxide Percure HI (manufactured by NOF Corporation, trade name) 1.0 part by mass, 0.77 part by mass of polymerization inhibitor parabenzoquinone, and release agent An unsaturated polyester resin composition was obtained by blending 2.5 parts by mass of zinc stearate, 2.0 parts by mass of magnesium oxide as a thickener, and 150 parts by mass of calcium carbonate as a filler. The unsaturated polyester resin composition obtained by blending in this manner was impregnated into glass fibers to produce SMC.

In addition, in order to produce a molded product with a pattern, in order from the surface mold side, materials are put in the order of a semi-cured resin sheet with a pattern and SMC into a mold, and a 200 mm square molded product is formed by heat and pressure integral molding. Obtained. The molding conditions were as follows: SMC input weight 400 g, molding pressure 5.88 MPa, holding time 3 minutes, and the surface mold used was a mold with fine irregularities with an average depth of 50 μm and 200 μm. .

Example 1
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide paroyl TCP (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added.
A glass paper having a basis weight of 30 g / m ² is laminated as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm formed by gravure printing and patterned on one side by regular printing. Then, a clear film was placed, rolled and pressed by a roller, defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 50 μm to obtain a patterned product.
(Example 2)
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure O (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added.
A glass paper having a basis weight of 30 g / m ² is laminated as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm formed by gravure printing and patterned on one side by regular printing. Then, a clear film was placed, rolled and pressed by a roller, defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 50 μm to obtain a patterned product.
(Example 3)
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure AL (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added.
A glass paper having a basis weight of 30 g / m ² is laminated as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm formed by gravure printing and patterned on one side by regular printing. Then, a clear film was placed, rolled and pressed by a roller, defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 50 μm to obtain a patterned product.
Example 4
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure AL (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution and 0.4 parts by mass of chain transfer agent NOFMER MSD (trade name, manufactured by NOF Corporation) were blended.
A glass paper having a basis weight of 30 g / m ² is laminated as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm formed by gravure printing and patterned on one side by regular printing. Then, a clear film was placed, rolled and pressed by a roller, defoamed and impregnated. Thereafter, it was cured at 70 ° C. for 20 minutes to obtain a semi-cured patterned semi-cured resin sheet. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 50 μm to obtain a patterned product.
(Example 5)
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure AL (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added.
A glass paper with a basis weight of 30 g / m ² is layered as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm, which is patterned by regular printing on one side by inkjet printing, and further contains a composition. Then, a clear film was placed, rolled and pressed by a roller, defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 50 μm to obtain a patterned product.
(Example 6)
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure AL (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added. On the clear film, a printed nonwoven fabric with a pattern prepared by patterning one side by gravure printing was placed, and further, the blended composition and the clear film were placed, rolled and pressed by a roller, and defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 50 μm to obtain a patterned product.
(Example 7)
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure AL (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added.
A glass paper having a basis weight of 30 g / m ² is laminated as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm formed by gravure printing and patterned on one side by regular printing. Then, a clear film was placed, rolled and pressed by a roller, defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 200 μm to obtain a patterned product.
(Example 8)
Unsaturated polyester resin PS-3717 (trade name, manufactured by DH Material Co., Ltd.) on the patterned surface of a transfer film having a thickness of 50 μm formed by pattern printing on one side by regular printing by gravure printing. 100 mass parts, organic peroxide paroyl TCP (Nippon Yushi Co., Ltd. product name) 1.0 mass part, Percure O (Nippon Yushi Co., Ltd. product name) 0.5 mass part was further mixed. A clear film was placed thereon and rolled and pressed by a roller to defoam and impregnate. Curing was carried out at 70 ° C. for 10 minutes to form a pattern fixing layer. Furthermore, 100 parts by mass of unsaturated polyester resin PS-9117 (trade name, manufactured by DH Material Co., Ltd.), 0.5 parts by mass of organic peroxide percure AL (trade name, manufactured by NOF Corporation), dissolved in triethyl phosphate 0.3 parts by weight of a 10% ascorbic acid solution was added and placed on a pattern fixing layer prepared in advance, and glass paper and a clear film with a basis weight of 30 g / m ² were placed on the pattern fixing layer. Rolled and pressed, defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 200 μm to obtain a patterned product.
Example 9
Unsaturated polyester resin PS-3717 (manufactured by DH Material Co., Ltd.) on the printing surface of a transfer film with a thickness of 50 μm, which was patterned by reverse printing on one side by gravure printing and formed a pattern on the clear film side Name) 100 parts by mass, organic peroxide paroyl TCP (Nippon Yushi Co., Ltd., trade name) 1.0 part by mass, Percure O (Nippon Yushi Co., Ltd., trade name) 0.5 parts by mass was mixed. Further, a glass paper with a basis weight of 30 g / m ² and a clear film were placed thereon, and rolled and pressed by a roller to defoam and impregnate. Curing was performed at 70 ° C. for 10 minutes, a pattern fixing layer was formed, and the clear film on the pattern layer side was peeled off. Furthermore, 100 parts by mass of unsaturated polyester resin PS-9117 (trade name, manufactured by DH Material Co., Ltd.), 0.5 parts by mass of organic peroxide percure AL (trade name, manufactured by NOF Corporation), dissolved in triethyl phosphate 0.3 parts by weight of a 10% ascorbic acid solution was added and placed on a pattern layer of a pattern fixing layer prepared in advance, and further a glass paper and a clear film with a basis weight of 30 g / m ² were placed thereon. Then, it was rolled and pressed by a roller, and defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 200 μm to obtain a patterned product.
(Example 10)
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure AL (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added. On the clear film, place one side of the printed nonwoven fabric with a gravure pattern on it and place it in the order of glass paper with a basis weight of 30 g / m ^2. And defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 200 μm to obtain a patterned product.
(Example 11)
Unsaturated polyester resin PS-9117 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure AL (manufactured by Nippon Oil & Fats Co., Ltd., trade name) 0.5 parts by mass, dissolved in triethyl phosphate 0.3 parts by mass of 10% ascorbic acid solution was added.
A glass paper having a basis weight of 30 g / m ² is laminated as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm formed by gravure printing and patterned on one side by regular printing. Then, a clear film was placed, rolled and pressed by a roller, defoamed and impregnated. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. A pattern is obtained by placing a non-woven fabric between the patterned semi-cured resin sheet thus obtained and the SMC, and performing pressure heating and integral molding using a mold having an average depth of 200 μm on the surface. A molded article was obtained.
(Comparative Example 1)
SMC was pressure-heat-molded using the type | mold whose surface unevenness | corrugation average depth is 50 micrometers, without using a semi-cured resin sheet with a pattern, and the SMC molded article was obtained.
(Comparative Example 2)
Unsaturated polyester resin PS-3717 (manufactured by DH Material Co., Ltd., trade name) 100 parts by mass, organic peroxide Percure O (manufactured by Nippon Oil & Fats Co., Ltd., trade name), 0.5 parts by mass, Parroyl TCP (Nippon Oils and Fats) Product name) 1.0 part by mass was blended.
A glass paper having a basis weight of 30 g / m ² is laminated as a reinforcing layer on the patterned surface of a transfer film having a thickness of 50 μm formed by patterning on one side by gravure printing, and further, a blending composition and a clear film Was rolled and pressed with a roller to defoam and impregnate. Then, after making it harden | cure at 70 degreeC for 10 minutes, the semi-hardened resin sheet with a pattern of the semi-hardened state was obtained by cooling at 5 degreeC. The patterned semi-cured resin sheet thus obtained was integrally molded with SMC under pressure and heat using a mold having an average depth of surface irregularities of 50 μm to obtain a patterned product.

(Test method)
(1) Evaluation of handleability The surface of the obtained semi-cured resin sheet with a pattern is touched by hand, ○ when there is no stickiness, △ when there is stickiness, and when the clear film does not peel × As evaluated.
(2) Transfer rate measurement method The surface of the obtained molded product was evaluated with a surface roughness shape measuring machine Surfcom 130A (manufactured by Tokyo Seimitsu Co., Ltd.), an evaluation length of 20 mm, a measurement speed of 0.6 mm / s, and a cutoff value of 0. 0.08 mm, filter type Gaussin, cutoff ratio 300, and the average value of arithmetic average roughness Ra (JIS B0601-1994) when measuring three or more arbitrarily selected points is calculated, and the transfer rate for the mold is calculated. did. The case where the transfer rate was 90% or more was rated as ◯, the case where it was 70% or more and less than 90%, and the case where it was less than 70%.
(3) Evaluation of pattern sharpness The pattern sharpness of the obtained molded product was visually determined. A case where the pattern was clear was indicated by ◯, a case where the pattern was blurred was indicated by △, and a case where the shape of the pattern was not known was indicated by ×.
(4) Evaluation of designability The designability and appearance of the obtained molded product were visually determined. The case where the designability was excellent was evaluated as ◯, the case where there was not much designability as △, and the case where there was no designability as X.

  As a result, the patterned semi-cured resin sheet in the above example was easy to handle because it was not sticky and flexible. In addition, it has strength and flexibility that does not cause outflow, crack breakage, etc., due to the flow of molding material during pressure heating integrated molding, and reaction that only allows adhesion to the molding material when fully cured Since the group remains, adhesion to the molding material was also ensured. In addition, ascorbic acid and organic peroxide are blended so that the maximum exothermic peak temperature is 110 ° C. to 180 ° C. when DSC measurement is performed at a temperature rising rate of 10 ° C./min. Compared to conventional semi-cured resin sheets with a low-temperature decomposition type organic peroxide that forms a semi-cured state, flexibility can be maintained longer, and fine unevenness, gloss, and matte on the mold surface. A patterned semi-cured resin sheet having good conformability to the shape and good transfer rate was obtained. On the other hand, the sharpness of the pattern was maintained by forming the pattern fixing layer on the mold surface with deep irregularities. In addition, the patterned semi-cured resin sheet of the present invention has no pattern restrictions such as pattern color, wood grain, stone tone, abstract pattern, etc., and is excellent in pattern sharpness and suitable for the production of patterned molded products. It was.

It is sectional drawing which shows the molded article with a pattern of this invention. It is a figure which shows the manufacturing method at the time of using the printed transfer film of the semi-cured resin sheet with a pattern of this invention. It is a figure which shows the manufacturing method at the time of using the printed reinforcement layer of the semi-cured resin sheet with a pattern of this invention. It is a figure which shows the manufacturing method at the time of forming the pattern fixing layer using the printed transfer film of the semi-cured resin sheet with a pattern of this invention. It is a figure which shows the manufacturing method of the molded article with a pattern of this invention. It is a figure which shows the manufacturing method of the molded article with a pattern at the time of arrange | positioning a nonwoven fabric between the semi-hardened resin sheet with a pattern and SMC of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, Clear resin layer 2, Reinforcement layer 3, Transfer pattern layer 4, Base material layer 5, Pattern fixing layer 6, Pattern layer 7, Transfer pattern layer 8, Reinforcement material 9, Clear resin layer forming composition 10, Clear film 11 , Roller 12, pattern fixing layer forming composition
13, Patterned semi-cured resin sheet 14, Molding material 15, Surface mold 16, Back mold
17. Nonwoven fabric

Claims (13)

  A clear resin layer, a reinforcing layer, a pattern layer or a transfer pattern layer, or a pattern fixing layer is provided, the degree of cure of the clear resin layer is 5 to 80%, and the clear resin layer forming composition is 10 ° C. A patterned semi-cured resin sheet having a maximum exothermic peak temperature of 110 to 180 ° C. when DSC measurement is performed at a heating rate of / min.   The patterned semi-cured resin sheet according to claim 1, wherein the clear resin layer contains a thermosetting resin, an organic peroxide, and ascorbic acid.   The patterned semi-cured resin sheet according to claim 2, wherein the clear resin layer is brought into a semi-cured state at 30 to 100 ° C and then cooled to 10 ° C or lower.   The patterned semi-cured resin sheet according to claim 1, wherein the clear resin layer contains a thermosetting resin, an organic peroxide, ascorbic acid, and a chain transfer agent.   The patterned semi-cured resin sheet according to claim 4, wherein the clear resin layer is semi-cured at 0 to 100 ° C.   6. The patterned semi-cured resin sheet according to claim 1, wherein the reinforcing layer is formed by impregnating a clear resin layer forming composition into a woven fabric or a non-woven fabric.   The patterned semi-cured resin sheet according to any one of claims 1 to 6, wherein the pattern layer is formed by gravure printing or ink jet printing.   The patterned semi-cured resin sheet according to any one of claims 1 to 7, wherein the pattern layer or the transfer pattern layer is formed by laminating a glass fiber nonwoven fabric or a synthetic resin nonwoven fabric on the surface opposite to the reinforcing layer.   A molded product obtained by laminating the patterned semi-cured resin sheet according to any one of claims 1 to 8 on an SMC, and integrally forming under pressure and heating.   In Claim 9, SMC impregnates a fiber reinforcement with the compound containing a thermosetting resin, a polymerizable monomer, a low shrinkage agent, an organic peroxide, a polymerization inhibitor, a filler and a thickener. A fiber-reinforced molding material formed into a sheet.   The molded product according to claim 9 or 10, wherein the molded product has fine irregularities on a part or all of its surface.   The molded product according to claim 9, wherein the molded product is a bathroom component. The molded product according to any one of claims 9 to 12, wherein a glass fiber nonwoven fabric or a synthetic resin nonwoven fabric is disposed between the patterned semi-cured resin sheet and the SMC.

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